Diastereomeric Xe chemical shifts in tethered cryptophane cages

TitleDiastereomeric Xe chemical shifts in tethered cryptophane cages
Publication TypeJournal Article
Year of Publication2006
AuthorsRuiz E.J, Sears D.N, Pines A, Jameson C.J
JournalJournal of the American Chemical Society
Date PublishedDec 27
ISBN Number0002-7863
Accession NumberWOS:000242941600104

Cryptophane cages serve as host molecules to a Xe atom. Functionalization of cryptophane-A has permitted the development of Xe as a biosensor. Synthetic routes used to prepare cryptophanes result in racemic mixtures of the chiral cages. In the preparation of a tethered cryptophane-A cage for biosensor applications, some achiral and chiral substituents such as left-handed amino acids have been used. When the substituent is achiral, the NMR signal of the Xe atom in the functionalized cage in solution is a single isotropic peak, since the Xe shielding tensor components in the R and L cages differ by no more than the signs of the off-diagonal elements. Chiral substituents can split the cage-encapsulated Xe NMR signal into one or more sets of doublets, depending on the number of asymmetric centers in the substituent. We carry out quantum mechanical calculations of Xe nuclear magnetic shielding for the Xe atom at the same strategic position within an L cryptophane-A cage, under the influence of chiral potentials that represent for r or I substituents outside the cage. Calculations of the Xe shielding response in the Lr and LI diastereomeric pairs permit the prediction of the relative order of the Xe chemical shifts in solutions containing the RI and LI diastereomers. Where the substituent itself possesses two chiral centers, comparison of the calculated isotropic shielding responses in the Llr, Lrl, RIl, and Lrr systems, respectively, permits the prediction of the Xe spectrum of diastereomeric systems in solutions containing Llr, RIr, LIl, and RIl systems. Assignment of the peaks observed in the experimental Xe NMR spectra is therefore possible, without having to undertake the difficult synthetic route that produces a single optically pure enantiomer.

URL<Go to ISI>://WOS:000242941600104
Short TitleDiastereomeric Xe chemical shifts in tethered cryptophane cages
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